CN104559177B - The preparation method of resin combination and prepreg, composite base material and PCB substrate - Google Patents

Abstract

The invention discloses a method for preparing a resin composition, a prepreg, a composite substrate and a PCB substrate. The resin composition is composed of the following components in parts by weight: 70-90 parts of cyanate resin, fluorine-containing 10-30 parts of polymer, 0.01-0.05 parts of accelerator. The preparation method of the prepreg is to mix the resin composition with an organic solvent to obtain a resin solution, the resin solution has a solid content of 45% to 65% by mass, and immerse glass fiber cloth in the resin solution to obtain a prepreg , and then dry the prepreg to make the prepreg. The preparation method of the composite base material is formed by stacking and pressing the prepregs according to a predetermined number of sheets. The preparation method of the PCB base material is formed by stacking the prepregs according to a predetermined number of sheets, adding metal foil on both sides or one side, and pressing. The resin composition of the invention has high heat resistance, low dielectric loss and good toughness.

Description

Preparation method of resin composition, prepreg, composite substrate and PCB substrate

technical field

The invention relates to the field of polymer materials, in particular to a method for preparing a resin composition, a prepreg, a composite base material and a PCB base material.

Background technique

Cyanate resin is favored by many scientific researchers because of its excellent high temperature resistance and dielectric properties. Cyanate resin as the matrix has been widely used in composite substrates and high-frequency circuit boards. However, the triazine ring structure formed after cyanate ester curing provides excellent heat resistance and dielectric properties, and at the same time increases the brittleness of the substrate. The existing cyanate matrix composite materials are toughened and modified with epoxy resin, but the toughening of epoxy resin will lead to the reduction of dielectric and heat resistance properties. For this reason, it is a market trend to develop composite substrates that not only satisfy heat resistance, rigidity, but also flexibility and dielectric properties.

Contents of the invention

The technical problem to be solved by the present invention is to make up for the deficiencies of the above-mentioned prior art, and propose a method for preparing a resin composition, a prepreg, a composite base material, and a PCB base material. The resin composition has high heat resistance and low dielectric loss And has good toughness.

Technical problem of the present invention is solved by following technical scheme:

A resin composition is composed of the following components in parts by weight: 70-90 parts of cyanate resin, 10-30 parts of fluorine-containing polymer, and 0.01-0.05 parts of accelerator.

A method for preparing a prepreg. The resin composition is mixed with an organic solvent to obtain a resin solution, the solid content of the resin solution is 45% to 65% by mass, and glass fiber cloth is immersed in the resin solution to obtain a prepreg. prepreg, and then drying the prepreg to make the prepreg.

A method for preparing a composite base material. The prepregs are laminated according to a predetermined number of sheets and pressed to form the composite base material.

The invention relates to a method for preparing a PCB base material. The prepregs are laminated according to a predetermined number of sheets, and metal foil is applied on both sides or one side, and pressed to form the PCB base material.

The beneficial effects of the present invention compared with the prior art are: the present invention uses cyanate resin with excellent heat resistance as the masterbatch, and the cyanate resin is self-cured by heating to form a three-dimensional network structure of triazine ring space, with high cross-linking density, Ensure that the product has high heat resistance. Fluorine-containing polymer is used for toughening. After the addition of fluorine-containing polymer, cyanate ester, and accelerator are coordinated according to the proportion of the present invention, the product has heat resistance and low dielectric loss. And flexibility with good comprehensive effect.

Detailed ways

The present invention will be further described below in combination with preferred embodiments.

The present invention provides a resin composition. In one embodiment, the resin composition consists of the following components in parts by weight: 70-90 parts of cyanate resin, 10-30 parts of fluoropolymer, accelerator 0.01-0.05 parts.

In some preferred embodiments, at least one of the following schemes can also be adopted:

The cyanate resin is 75-80 parts; the fluoropolymer is 15-25 parts; the fluoropolymer is PTFE (polytetrafluoroethylene), FEP (polyfluoroethylene propylene), PFA ( One or more mixtures of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), ETFE (ethylene-tetrafluoroethylene copolymer) and ECTFE (ethylene-chlorotrifluoroethylene copolymer); the Cyanate resin is one or their combination in bisphenol A type cyanate ester prepolymer and polyfunctional cyanate resin; Described polyfunctional cyanate resin is linear polyfunctional cyanate resin, ortho Cresol type polyfunctional cyanate resin (i.e. poly-o-cresol cyanate resin) and dicyclopentadienol type cyanate resin or a combination of two or more, when using two or more When the composite resin of multifunctional cyanate resin is used, the prepreg made by impregnating it also has good leveling property and good appearance. body particles; the accelerator is an imidazole accelerator; the imidazole accelerator is 2-methylimidazole (2-MI), 2-ethyl-4-methylimidazole (2E4MI) and 2-phenylimidazole One or a combination of two or more of (2-PI).

The multifunctionality mentioned in the present invention means that the functionality is at least 3.

The resin composition of the present invention can be applied in adhesive sheets (or called prepregs), composite substrates, and PCB substrates.

When preparing adhesive sheets, the specific method is as follows:

Mix cyanate resin, fluorine-containing polymer, and accelerator according to the above ratio, and add them into an organic solvent to form the above resin solution. The amount of organic solvent is determined according to the solid content of the resin composition in the resin solution. The resin solution The mass fraction of the solid content is 45-65%. The glass fiber cloth is immersed in the above resin solution to obtain a prepreg, and then the prepreg is dried to make a semi-cured adhesive sheet. The prepared adhesive sheet has ideal adhesion and toughness, is suitable for cladding and forming of composite substrates, and has low dielectric loss, and is especially suitable for high-frequency circuit substrates.

Preferably, the conditions for drying the prepreg are: drying in an oven at 100-130° C. for 2-5 minutes, and then drying at 160-180° C. for 3-5 minutes.

Preferably, the organic solvent can be methyl ethyl ketone or acetone or a mixture of the two; when the solvent is a mixture of methyl ethyl ketone and acetone, the volume ratio of methyl ethyl ketone and acetone is 1:2 to 2:3, using such a mixed solvent can Increases the smoothness of the product.

When preparing the composite base material, the specific method is as follows: stack the adhesive sheets prepared above according to the set number of sheets, and press them to form a composite base material. Preferably, the pressing is performed at a temperature of 200±5° C. and a pressure of 25±5 kgf/cm ² .

When preparing the PCB base material, the specific method is as follows: stack the above-mentioned adhesive sheets according to the set number of sheets, add metal foil on both sides or one side, and press to form a PCB base material. Preferably, the pressing is carried out at a temperature of 200±5°C and a pressure of 25±5kgf/cm ² ; the metal in the metal foil can be copper, silver, gold, nickel, etc., preferably copper foil, and the prepared PCB substrate The material is called copper clad laminate.

The prepared composite base material and PCB base material have high heat resistance and flexibility, and are suitable as substrates for high-frequency circuits.

The present invention will be further elaborated below through more specific examples.

Embodiment one

Take by weighing the bisphenol A type cyanate ester prepolymer of 90 weight parts, the polytetrafluoroethylene powder of 10 weight parts and the 2-methylimidazole (2-MI) of 0.02 weight part, add in the butanone of 66 weight parts Prepare a resin solution with a solid content of 60% (mass fraction), that is, in the resin solution, the mass ratio of each component is: bisphenol A cyanate prepolymer: polytetrafluoroethylene: 2-methylimidazole: Butanone=90:10:0.02:66. Dip 6 pieces (250mm*250mm) of 7628 quartz cloth into the above resin solution for impregnation, bake in an oven at 130°C for 2 minutes and then at 160°C for 5 minutes to make a semi-cured adhesive sheet. The gel time (GT) of the tab is 105±15 seconds (171°C), and the fluidity is 25±5%. Superimpose and align the above six adhesive sheets, each with a 35μm copper foil on the top and bottom, press in a vacuum press for 120 minutes under the conditions of temperature 200°C and pressure 25kgf/ ^cm2 , and make a thickness of 1.2mm Double-sided copper clad laminate.

Embodiment two

Take by weighing 70 parts by weight of dicyclopentadiene phenol type cyanate resin, 30 parts by weight of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) powder and 2-ethyl-4- Methylimidazole (2E4MI), join in the acetone of 66 weight parts and be made into the resin solution that solid content is 60%, i.e. in the resin solution, the mass ratio of each component is: dicyclopentadienol type cyanate resin: PFA:2E4MI:acetone=70:30:0.01:66. Dip 6 pieces (250mm*250mm) of 7628 quartz cloth into the above resin solution for impregnation, bake in an oven at 130°C for 2 minutes and then at 160°C for 5 minutes to make a semi-cured adhesive sheet. The gel time (GT) of the tab is 105±15 seconds (171°C), and the fluidity is 25±5%. Superimpose and align the above 6 adhesive sheets, each with a 35μm copper foil, press in a vacuum press for 120 minutes at a temperature of 200°C and a pressure of 25kgf/ ^cm2 to make a thickness of 1.2mm Double-sided copper clad laminate.

In other embodiments, the parts by weight of cyanate resin can also be 75 parts, 78 parts, 80 parts, etc.; the parts by weight of fluoropolymer can also be 15 parts, 20 parts, 25 parts, etc.; A part can also be 0.03 part, 0.04 part, 0.05 part, etc.

Comparative example one

Take by weighing 200 grams of bisphenol A type cyanate ester prepolymer, 100 grams of bisphenol A type novolac epoxy resin and 0.008 gram of 2-methylimidazole, use acetone/butanone mixed solvent, be made into a solid content of 60% resin solution. Use 6 sheets (250mm*250mm) of 7628 quartz cloth to dip into the above resin solution for impregnation to make a semi-cured adhesive sheet. The gel time (G-T) of the adhesive sheet is 105 seconds (171°C), and the fluidity is 22%. Other conditions were the same as in Example 1, and a double-sided copper-clad laminate with a thickness of 1.2 mm was produced.

Comparative example two

Take by weighing the bisphenol A type cyanate ester prepolymer of 90 weight parts, the polytetrafluoroethylene powder of 10 weight parts and the catalyst manganese acetylacetonate of 250ppm/ every gram of resin, add in the butanone of 66 weight parts and be made into solid content 60% (mass fraction) resin solution. Dip 6 pieces (250mm*250mm) of 7628 quartz cloth into the above resin solution for impregnation, bake in an oven at 130°C for 2 minutes and then at 160°C for 5 minutes to make a semi-cured adhesive sheet. The gel time (GT) of the tab is 105±15 seconds (171°C), and the fluidity is 25±5%. Superimpose and align the above 6 adhesive sheets, each with a 35μm copper foil, press in a vacuum press for 120 minutes at a temperature of 200°C and a pressure of 25kgf/ ^cm2 to make a thickness of 1.2mm Double-sided copper clad laminate.

Comparative example three

Take by weighing 70 parts by weight of dicyclopentadiene phenol type cyanate resin, 40 parts by weight of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer powder and 2-ethyl-4-methylimidazole of 0.01 parts by weight (2E4MI), join in the acetone of 66 parts by weight and be made into the resin solution that solid content is 60%. Dip 6 pieces (250mm*250mm) of 7628 quartz cloth into the above resin solution for impregnation, bake in an oven at 130°C for 2 minutes and then at 160°C for 5 minutes to make a semi-cured adhesive sheet. The gel time (GT) of the tab is 105±15 seconds (171°C), and the fluidity is 25±5%. Superimpose and align the above 6 adhesive sheets, each with a 35μm copper foil, press in a vacuum press for 120 minutes at a temperature of 200°C and a pressure of 25kgf/ ^cm2 to make a thickness of 1.2mm Double-sided copper clad laminate.

Comparative example is compared with embodiment, and result is as shown in the table below:

It can be seen from the above table that the copper clad laminate made of the resin composition of the present invention not only has good toughness, but also has superior heat resistance and dielectric properties than the prior art.

The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be assumed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art to which the present invention belongs, several equivalent substitutions or obvious modifications can be made without departing from the concept of the present invention, and those with the same performance or use should be deemed to belong to the protection scope of the present invention.

Claims (10)

1. A resin composition, characterized in that it is made up of the following components in parts by weight: 70-90 parts of cyanate resin, 10-30 parts of fluoropolymer for toughening, 0.01-0.05 part of accelerator , the accelerator is an imidazole accelerator; the cyanate resin is a masterbatch, which is self-cured by heating to form a three-dimensional network structure of triazine ring space; the cyanate resin is a bisphenol A type cyanate prepolymerized One or their combination in compound and polyfunctional cyanate resin, described polyfunctional cyanate resin is linear polyfunctional cyanate resin, o-cresol type polyfunctional cyanate resin and dicyclopentadiene One or more combinations of phenolic cyanate resins; the fluoropolymers are polytetrafluoroethylene, polyperfluoroethylene propylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene - a mixture of one or two or more of tetrafluoroethylene copolymers and ethylene-chlorotrifluoroethylene copolymers; the imidazole accelerators are 2-methylimidazole, 2-ethyl-4-methylimidazole and One or a combination of two or more of 2-phenylimidazoles. 2. The resin composition according to claim 1, characterized in that: 75-80 parts of the cyanate resin and/or 15-25 parts of the fluorine-containing polymer. 3. The resin composition according to claim 1, characterized in that: the fluoropolymer is a powder particle with a particle size in the range of 1-30 microns. 4. A method for preparing a prepreg, characterized in that: the resin composition according to any one of claims 1-3 is mixed with an organic solvent to obtain a resin solution, and the mass fraction of the solid content of the resin solution is 45 to 65 %, immerse the glass fiber cloth in the resin solution to obtain a prepreg, and then dry the prepreg to make the prepreg. 5. The preparation method of the prepreg according to claim 4, characterized in that: the organic solvent is butanone or acetone or a mixture of the two. 6 . The method for preparing a prepreg according to claim 5 , wherein the solvent is a mixture of butanone and acetone, and the volume ratio of the butanone and acetone is 1:2˜2:3. 7. A method for preparing a composite base material, characterized in that: the prepregs prepared by the preparation method according to any one of claims 4-6 are stacked according to a predetermined number of sheets, and pressed to form the composite base material. 8 . The preparation method of the composite substrate according to claim 7 , wherein the pressing is carried out at a temperature of 200±5° C. and a pressure of 25±5 kgf/cm ² . 9. A method for preparing a PCB base material, characterized in that: the prepregs prepared by the preparation method described in any one of claims 4-6 are stacked according to a predetermined number of sheets, and metal foil is added on both sides or one side , pressed into the PCB substrate. 10. The method for preparing PCB base material according to claim 9, characterized in that: said pressing is carried out at a temperature of 200±5°C and a pressure of 25±5kgf/cm ² .